Herbicidal 2-aryl-4,4-dialkyl-5-halomethylene-oxazolines

ABSTRACT

Biocidal compositions which contain as the active ingredient a compound belonging to the class of 2-(mono, di or trisubstituted-phenyl)-4,4-dialkyl-5-halomethylene-oxazolines and their salts and their use in controlling plant growth and phytopathogenic fungi.

United States Patent [191 McNulty et al.

[ June 25, 1974 [73] Assignee: Rohm and Haas Company,

Philadelphia, Pa.

22 Filed: Apr. 19, 1971 211 Appl. No.: 135,483

Related US. Application Data [62] Division of Ser. No. 829,084, May 29, 1969, Pat. No.

[52] US. Cl. 71/88 [51] Int. Cl AOln 9/00 [58] Field of Search 71/88 [56] References Cited FOREIGN PATENTS OR APPLICATIONS 1,545,928 10/1968 France OTHER PUBLlCATlONS Goodman et al., J. Am. Chem. Soc., 79, 4789 (1957). Fahey et al., J. Am. Chem. Soc., 88, 55555 (1966).

Primary Examiner-James 0. Thomas, .1 r.

[57] ABSTRACT Biocidal compositions which contain as the active ingredient a compound belonging to the class of 2- (mono, di or tri-substituted-phenyl)-4,4-dialkyl-5- halomethylene-oxazolines and their salts and their use in controlling plant growth and phytopathogenic fungi.

4 Claims, No Drawings HERBICIDAL 2-ARYL-4,4-DIALKYL-S-HALOMETHYLENE- OXAZOLINES This application is a divisional of US. Pat. Ser. No. 829,084, filed May 29, 1969 now US. Pat. No.

2 N-( l, l -dimethyl-3-chloroacetonyl )-3- chlorobenzamide N-( l l-diethyl-3-chloroacetonyl )-3-chlorobenzamide N-( l l-dimethyl-3-chloroacetonyl )-3,5-

5 dichlorobenzamide wherein X and X are selected from the group consisting of hydrogen, bromo, chloro, fluoro, methyl, ethyl and trifluoro-methyl groups with the proviso that only one of X and X may be hydrogen;

Y is hydrogen, bromo, chloro, fluoro or methyl;

R and R are individually selected from the group consisting of methyl and ethyl; and

n is an integer from 0 to 2 inclusive.

At times these compounds will hereinafter be referred to as N-(l,l-dialkyl-3-chloroacetonyl) benzamides.

The novel compounds of this invention provide a new class of selective herbicides. They are effective at low dosage rates and are particularly active by preemergence-type application. Many of the major economic crops are tolerant to them. These compounds also possess fungicidal activity, particularly against Phycomycetes.

Somewhat related structures are known in the literature. Gabriel, Berichte 46, 1319 (1913) reported the preparation of C H CONHC(CH COCH by hydrolysis of the corresponding tetramic acid ester. These compounds are not known to be biological toxicants.

The novel N-( l ,1-dia|kyl-3-chloroacetonyl) benzamides are of three types, monochloro (Formula II), di-

chloro (Formula Ill) and trichloro (Formula IV):

m wQ-okommiziomer R X (I!) R! c Y- -o o Nm'J-bo1w1,

l l Y- -o 0)NH( :-oocn R: X (IV) Typical compounds within the scope of Formula I include the following:

N-( l,l-dimethyl-3-chloroacetonyl)-3-bromo-5- chlorobenzamide N-( l l -dimethyl-3-chloroacetonyl )-3-chloro-5- methylbenzamide N-( l,l-dimethyl-3-chloroacetonyl )-3-fluoro-5- methylbenzamide N-( l l-dimethyl-3 chloroacetonyl)-3-ethyl-5- methylbenzamide N-( l l -dimethyl-3-chloroacetonyl )-3-chloro-4- methylbenzamide N-( l ,l-dimethyl-3-chloroacetonyl)-3 ,4,5- trichlorobenzamide N-( 1 ,1-dimethyl-3-chloroacetonyl)-3,5-dichloro-4- methylbenzamide N-( l,l-dimethyl-3-chloroacetonyl)-3,5-dibromo-4- chlorobenzamide N-( l l -dimethyl-3,3-dichloroacetonyl)-3- chlorobenzamide N-( l l-dimethyl-3,3-dichloroacetonyl)-3- ethylbenzamide N-( l,l-dimethy1-3,3-dichloroacetonyl )-3- fluorobenzamide N-( l, l -dimethyl-3,3-dichloroacetonyl)-3- methylbenzamide N-( l ,l-dimethyl-3,3-dichloroacetonyl)-3-chloro-4- methylbenzamide N-( l ,1-dimethyl-3,3-dichloroacetonyl)-3,S-dimethylbenzamide N-( l, l -dimethyl-3,3-dichloroacetonyl)-3,4,5- trichlorobenzamide N-( l, l -dimethyl-3,3-dichloroacetonyl )-3 ,5-dichloro-4- methylbenzamide N-( l ,l-dimethyl-3,3-dichloroacetonyl)-3,5-dichloro-4- bromobenzamide N-( l l-dimethyl-3,3,3-trichloroacetonyl)-3- chlorobenzamide N-( l,l-dimethyl-3 ,3,3-trichloroacetonyl )-3- methylbenzamide N-( l, l -dimethyl-3,3,3-trichloroacetonyl )-3- bromobenzamide N-( l,l-dimethyl-3 ,3,3-trichloracetonyl )3-trifluoromethylbenzamide N-( l, l -dimethyl-3,3,3-trichloroacetonyl )-3-chloro-4- methylbenzamide N-( l,l-dimethyl-3,3,3-trichloroacetonyl)-3,5-dimethylbenzamide N-( 1 l-dimethyl-3,3,3-trichloroacetonyl)-3-chloro-5- fluorobenzamide N-( l l-dimethyl-3,3,3-trich1oroacetonyl)-3,4,5- trichlorobenzamide N-( 1,l-dimethyl-3,3,3-trichloroacetonyl)-3,5- dichloro-4-methylbenzamide N-( l,1-dimethyl-3,3,3-trichloroacetonyl)-3,4,5-trimethylbenzamide The novel N-( l,1-dialkyl-3-chloroacetonyl) benzamides of Formula Il may be prepared by the chlorination of the corresponding N-(l,l-dialkyl-2-propynyl) benzamide (Formula V), which produces a 2-phenyl- 4,4-dialkyl-S-chloromethylene-oxazoline (Formula VI), usually as the hydrochloride, and this is then hydrolyzed to the N-(l,l-dialkyl-3-chloroacetonyl) benzamide (Formula II). The following equation depicts this reaction:

This amidation reaction is conveniently carried out in the presence of an inert organic solvent in the temperature range of 0 to 50 C.

When a compound of Formula II is desired, the chlorination of a compound of Formula V is carried out in the presence of a solvent in which the starting benzamide (Formula V) is substantially soluble, but in which the oxazoline hydrochloride of Formula VI is essentially insoluble. In this manner the oxazoline hydrochloride is removed from the sphere of the reaction and overchlorination is avoided. Otherwise compounds of 40 Formula VII result. Suitable solvents for this reaction include ethers, such as ethyl ether and dioxane; chlorinated solvents, such as ethylene dichloride; and esters such as ethyl acetate. In preparing the monochloroacetonyl derivatives (Formula II) the use of an excess of chlorine is to be avoided. Other chlorinating agents, such as N-chlorosuccinimide and sulfuryl chloride, may be used, but chlorine is preferred. A catalyst such as phosphorus trichloride sometimes aids the reaction. The chlorination reaction may be run in the temperature range of 50 250 C, preferably 0 100 C. In cases where the nitrogen atom of the oxazoline ring is highly sterically hindered, the hydrochloride of the oxazoline does not precipitate and care must be taken to avoid overchlorination. In these cases the chloromethylene oxazoline (the free base of a Formula VI compound) is isolated upon removal of the solvent.

The hydrolysis of compounds of Formulas VI is readily carried out with water using a water-miscible solvent, such as an alcohol, e. g., ethanol, dioxane or acetic acid, preferably with acidic catalysts. If desired, a mineral acid such as hydrochloric or sulfuric acid, may be used to facilitate the reaction. The hydrolysis may be run in the temperature range of room temperature to reflux. The hydrolysis times will vary from a few minutes to several days depending upon the oxazoline hydrochloride being hydrolyzed, the temperature of hydrolysis and the solvent. Optimum conditions vary for the specific hydrolysis to be undertaken. It is desirable to avoid conditions which would give hydrolysis at the amide likage of the desired benzamide into its component parts. One convenient method for isolating the benzamides of Formula II is to add water to the reaction mixture in such an amount to just start precipitation and to allow the product to crystallize out. In this manner products requiring no further purification are often isolated.

Goodman and Winstein, J. Am. Chem. Soc. 79, 4789 (1957) have reported on the hydrolysis of a related oxazolinium bromide. They noted that the cleavage of the ring occurred at the ON linkage and resulted in a benzoic acid ester rather than a benzamide.

A compound of the type of Formula III may be prepared by the chlorination of a compound of Formula VI to give a 2-phenyl-4,4-dialkyl-5-chloro-5- dichloromethyl-oxazoline hydrochloride, which upon hydrolysis gives an N-( l,l-dialkyl-3,3-dichloracetonyl) benzamide (Formula III). The following equation depicts this:

Elf? Y C O=CHCI (VII) 9 H30 1 Formula III The chlorination of a compound of Formula VI is preferably run in a solvent. Solvents of the class of chlorinated hydrocarbons, such as carbon tetrachloride, ethers and esters are suitable. Chlorine is the preferred chlorinating agent although other chlorinating agents well known in the art may be used. Excesses of the chlorinating agent up to two times the calculated amount may be used. The reaction temperature may be in the range of -50 250 C, preferably 0 C.

The hydrolysis of a compound of Formula VII to give a compound of Fonnula III is carried out in the same manner as described above for the hydrolysis of a compound of Formula VI.

A compound of Formula IV may be produced by the chlorination of a compound of Formula II or III. The chlorination is preferably run in a solvent such as a chlorinated hydrocarbon, e.g., carbon tetrachloride, an ether or an ester. The reaction temperature may be in v therange of 50 250 C, preferably 100 C. A

catalyst such as ultraviolet light, ferric chloride or benzoylperoxide may be used to facilitate the reaction.

An alternate method for the preparation of the compounds of Formula I is by the chlorination of the parent N-( 1,1-dialkyl-3-acetonyl) nuclear-substituted benzamide. The following equation depicts this:

at Y --C(0)NHC-CCH; C1, FormulaI (VIII) EXAMPLE 8 Preparation of N-( l ,1-dimethyl-I i-chloroacetonyl)-3,5- dichlorobenzamide a. Preparation of 2-(3,5-dichlorophenyl)-4,4- dimethy1-5-chloromethylene-oxazoline hydrochloride A stream of chlorine was rapidly passed into a solution of N-(1,1-dimethylpropynyl)-3,5- dichlorobenzamide (200 g., 0.782 mole) in ethyl acetate (600 ml.) at 60 C., with stirring until the theoretical amount (55.4 g., 0.78 mole) was absorbed as measured by an in-line flow meter. During the addition a solid separated and after cooling was filtered off and dried to give 254.4 g. of solid melting at 154 157 C. This was a quantitative yield of 2-( 3,5-dichlorophenyl)- 4,4-dimethyl-5-chloromethylene-oxazoline hydrochloride.

b. Preparation of N-( l l -dimethyl-3- chloroacetonyl)-3,S-dichloro benzamide 2-(3,S-Dichlorophenyl)-4,4-dimethyl-5- chloromethylene-oxazoline hydrochlroide (245 g.,

0.75 mole) was heated on a steam bath for 25 minutes in a mixture of ethanol (1,750 ml.), water (500 ml.), and a solution of concentrated hydrochloric acid (30 ml.) in water (100 ml. More water (500 ml.) was then added and the solution set aside to cool. Needles separated and were filtered off to give 153.5 g. of solid melting at 161 C. After recrystallization from aqueous methanol, it melted at 161 to 163 C. The product was a 63 percent yield of N-(l,l-dimethyl-3- chloroacetonyl )-3 ,S-dichlo robenzamide.

EXAMPLE 13 Preparation of N-( 1,1-dimethyl-3,3-dichloroacetonyl)- 3,5-dichlorobenzamide a. Preparation of 2-(3.5-dichlorophenyl)-4,4- dimethyl-S-chloro-5-dichloromethyl-oxazoline hydrochloride and its free base Excess chlorine was passed into a solution of N-(1,1- dimethylpropynyl)-3.5-dichlorobenzamide (25.6 g.. 0.1 mole) in carbon tetrachloride (250 m1.) heated under reflux. On cooling, crystals separated and were filtered off to give 34 g. of solid. This was an percent yield of 2-(3,5-dichlorophenyl)-4,4-dimethy1-5-chloro- 5-dichloromethyl-oxazoline hydrochloride.

A small sample of this oxazoline hydrochloride was treated in ether with aqueous sodium carbonate to give the free base. The product was recrystallized from hexane to give a solid melting at 94 95 C. It was found to contain by analysis 40.5% C, 2.6% H, 48.7% Cl, 38% N and 5.1% 0; calculated for c l-l Cl NO is 39.0% C, 2.8% H, 49.0% C], 3.9% N and 4.4% O. The product is 2-(3,5-dichlorophenyl)-4,4-dimethyl-5- chloro-S-dichloromethyl-oxazoline.

b. Preparation of N-( l 1 -dimethyl-3 ,3- dichloroacetonyl)-3,5-dichlorobenzamide.

2-(3,5-Dichlorophenyl)-4,4-dimethyl-5-chloro-5- dichloromethyl-oxazoline hydrochloride (106 g., 0.266 mole.) was heated under reflux in ethanol (1,500 ml.) in the presence of concentrated hydrochloric acid (10 ml.) and water (65 ml.) for 30 minutes. The mixture was then diluted with water (350 m1.) and allowed to cool. A solid separated and was filtered off giving 65 g. of solid melting at 155 to 157 C. This was a 64 percent yield of N-(1,l-dimethyl-3,3-dichloroacetonyl)- 3,5-dichlorobenzamide.

EXAMPLE 14 Preparation of N-( 1,1-dimethyl-3 ,3 ,3- trichloroacetonyl)-3,5-dichlorobenzamide.

Chlorine was passed into a mixture of 70% N-( 1,1- dimethyl-3,3-dichloroacetonyl)-3,5- dichlorobenzamide and 30% N-( 1,1-dimethyl-3- chloroacetonyl)-3,5-dichlorobenzamide (52.5 g.) in carbon tetrachloride (525 ml.) at 55 C, while the solution was irradiated with an ultraviolet lamp. After the theoretical quantity of chlorine had been absorbed, the solution was allowed to cool and crystals separated and were filtered off to give 25 g. of solid melting at 137.5" 140 C. Recrystallization from benzene gave 14.5 g. melting at 144 l44.5 C. The product was a 42 percent yield of N-l,l-dimethyl-3,3,3-trichloroacetonyl)- 3,5-dichlorobenzamide.

EXAMPLE 15 Preparation of N-( 1 l -diethyl-3-chloroacetonyl)-3 ,5- dichlorobenzamide.

a. Preparation of N-( l,l-diethylpropynyl)-3,5- dichlorobenzamide.

An ether solution of 3,5-dichlorobenzoyl chloride (47 g., 0.225 mole) was allowed to react with 25 g. (0.225 mole) of 3-ethyl-3-aminopent-l-yne (available by the method of Hennion and Teach, .1. Am. Chem. Soc. 75, 1653 (1953), boiling point 114- 118 C.) in the presence of 18 g. (0.0225 mole) of 50 percent aqueous sodium hydroxide solution. The isolated product was recrystallized from benzene/hexane to give 42.5 g. of white solid melting at 98 to C. It was found by analysis to contain 59.5% C, 5.3% H, 4.9% N, 5.8% O and 24.6% C1; calculated for C H,,,CI NO is 59.2% C, 5.3% 1-1, 4.9% N, 5.6% O and 24.9% C1. The product is a 69 percent yield of N-(1,ldiethylpropynyl)-3,5-dichlorobenzamide.

b. Preparation of 2-(3,S-dichlorophenyl)-4.4-diethyl- 5-chloromethylene-oxazoline.

A stream of chlorine was rapidly passed into a solution of N-( 1,1-diethylpropynyl )-3 ,5- dichlorobenzamide (14.2 g., 0.05 mole) in 300 ml. of diethyl ether until the theoretical amount (3.6 g.. 0.05

E CF H H CH CH 126-129 F"" C H H H CH; CH gummy solid G Br Br H CH CH 140-148 H C1 C1 H CH CH;, 154-157 1" C1 C1 H CH CH 119-121 .1 C1 F H CH CH 158-159 K CH CH H CH CH 175-177 L" C1 C1 H CH C H oil M Cl H C1 CH CH 151-155 N C1 H F CH; CH;, 151-153 a. melting point of N-( 1.1-dimethylpropynyl )-3-hromobcnzamidc is 122 to 123 tlabfing ltcing point of N-(1.1-dimethylpropynyl)-3-fluorobenzamidc is 135.5" to c. N-(1,l-dimelhylpropynyll-3-clhylbenzamidc is an oily solid. d. free base TABLE 11 Analvtical Data" on Oxazo Empirical Preparation" Formula 7r C H N 7c 0 Halogen A C,,H,,BrClNO'HCl 43.0 (42.8) 3.5 (3.6) 4.1 (4.2) 5.0 (4.8) Cl, 20.7 (21.0) Br, 24.1 (23.7) B C. H,,C1 NO-HC1 49.1 (49.8) 4.5 (4.2) 4.8 (4.8) 8.4 (5.5) CI, 34.8 (35.7) C C H CIFNO-HCI 52.3 (52.3) 4.3 (4.4) 5.1 (5.1) CI, 25.6 (25.7)

' F, 6.6 (6.9) D C|=iH ,ClNOHCl 57.1 (57.4) 5.7 (5.6) 5.1 (5.1) 6.3 (5.9) Cl, 26.6 (26.1) E CmH CIF NO'HCl 45.7 (47.9) 3.8 (3.7) 4.0 (4.3) Cl, 20.6 (21.7) F C H ClNO 51.1 (52.4) 5.4 (5.0) 3.9 (4.3) 7.5 (5.0) C1, 32.1 (33.1) G C H Br NOHCl 37.4 (34.6) 2.6 (2.7) 3.5 (3.4) 5.4 (3.9) Br, 37.6 (38.4) H C H CI NOHCI 45.9 (44.0) 3.4 (3.4) 4.5 (4.3) 4.6 (4.9) Cl, 39.4 (43.4) 1 C H CI NO 49.5 (49.6) 3.6 (3.5) 4.6 (4.8) 5.8 (5.5) Cl, 36.2 (36.6) J C HmChFNOHCl 46.2 (46.4) 3.8 (3.6) 4.5 (4.5) C1, 33.9 (34.2)

F, 5.9 (6.1) K C H ClNO'HCl 58.5 (58.7) 6.1 (6.0) 4.8 (4.9) 6.0 (5.6) Cl, 24.5 (24.8) L C H C1 NO 52.5 (52.8) 4.6 (4.4) 4.2 (4.4) 4.9 (5.0) Cl, 33.6 (33.4) M C ,H, Cl,-,NO'HC1 44.9 (44.1) 3.4 (3.4) 4.3 (4.3) 5.2 (4.9) Cl. 42.6 (43.4) N C H Cl FNOHCl 46.4 (46.4) 4.0 (3.6) 4.3 (4.5) CI, 33.3 (34.2) V F,5.8(6.1)

a See Tablcl b Figures in parentheses are those calculated from the empirical formula.

drochloric acid. Water (200 ml.) was then added and Table 11 the gummy precipitate was washed free of starting material with pentane to give 3.5 g. of solid melting at 172.5 176 C. The product was a 28 percent yield of N-( 1,l-diethyl-3-chloroacetonyl)-3,5- dichlorobenzamide.

Tables 1 and 11 give the identity and physical characteristics of typical oxazolines and the hydrochloride salts used to prepare the benzamides of this invention.

Tables 111, IV and V give the identity and physical characteristics of typical examples of the benzamides of this invention.

Table 1 Oxazoline Hydrochlorides (or their free bases) of the Formula Compounds of the Formula Compounds of the Formula per hectare). Four types of monocotyledonous plants were used and these were wild oat (Avena fatua), millet (Setaria italica), ryegrass (Loliumperenne) and sor- R o rro-donncih.

Percent O Melting n Point (C) TABLE V Analytical data on benzamldes of the structure:

i Y- --C N Percent 0 Percent H Percent N Table lV-Continued 13 'CH, C11,. 14 CH CH;, 15 C,H, C H,

Empirical formula Example Example tomato flax velvetleaf nmwmmmmam mmmmw rammrmeau warea (c curly sorghum deck Table VI c Kill Preerner enc t sts es rn r Kill anemmaomomwonnm aofiouwowaodoood ghum (Sorghum vulgar-e). Four types of dicotyledonous plants were used and these were curly dock (Rumex crispus), velvetleaf (Abutilon Theophrasti). flax (Linum usitatissimum) and tomato (Lycopersicon esculentum). About two weeks after application of the test compounds, the state of growth and the phytotoxic effects were evaluated. Table VI gives the results.

Preliminar Herbicidal Evalu' tions millet ryegrass Wlld Example oat CrzHuChNO: CnHuCIFNO: CuHreClNOl uHnClFaNO: CuHnClNO: CuHuBhClNOI CraHnChNOl CuHnChFNO: CraHrrClANO: CuHmCIsN I CuHnClsNO:

I Figures in parentheses are those calculated from the emplriealjorrnula The compounds of this invention were evaluated in a standard greenhouse test known as a preliminary herbicial evaluation. For these tests seeds of selected crops and weeds were planted in soil in pots. For preemergence tests, these pots were treated immediately with 35 the test compound. For postemergence tests, the seeds were allowed to germinate and the plants to grow for Table VI demonstrates the good hermicial activity of compounds of Formula I. In similar tests compounds of Formula VII], the unchlorinated precursors, were found to have low herbicidal activity.

Similar preemergence and postemergence greenhouse tests were then run in a secondary type herbicidal test using a lower rate of application and more plant species planted in flats. For this test the amount of toxicant was 4 pounds per acre (4.4 kilos per hectare). The plant species used were:

Monocotyledonous Plant Botanical Name A crabgrass Digitaria sanguinalis B millet Setaria italica C wheat Triticum aestivum Q flax Linum usitassimum R' alfalfa Medicago sativa S tomato Lycopersicon esculentum T cotton Gossypium hirsutum Table VII gives the results.

Thisrnethod could beimportant in special applications,

TABLE VII.SECONDARY HERBICIDAL EVALUATIONS (4 lbs/A). PERCENT KILL OF PLANT SPECIES, PREEMERGENCE TESTS 100 90 60 0 60 90 0 0 70 40 90 so 40 90 o 0 0 0 2 100 mo 0 100 20 80 80 30 0 so 60 100 so 0 100 0 20 0 70 3 100 100 0 70 20 90 90 80 0 90 0 90 so so 100 0 0 60 4 90 90 o 90 30 so so 0 0 so 0 100 90 30 100 0 40 30 0 2 7 so 80 0 0 I0 40 80 0 0 0 0 0 90 0 100 0 0 60 0 8 s0 90 0 0 20 60 so 0 1o 20 40 50 50 0 90 0 20 40 20 9 90 100 0 so 20 90 90 so 20 70 so 100 100 30 100 0 40 40 70 10 90 90 0 50 20 so 90 0 0 0 so 90 50 0 100 0 0 0 20 I2 90 90 0 80 I0 80 90 80 I0 20 0 100 60 1o 50 20 40 40 so 14 60 70 0 0 0 30 so 0 0 0 0 90 0 100 80 0 0 0 0 s POSTEMERGENCE TESTS 9 so 10 40 20 10 10 40 0 0 90 70 so 0 30 0 0 0 I3 50 0 0 0 30 0 0 0 0 so 0 50 0 0 0 0 l5 0 0 20 0 0 0 20 0 I0 50 0 20 I0 0 20 0 10 g y k v such as where furrow irrigation lS practiced.

gifl fi :fdanensis In carrying out this test the seeds were planted m soil G: barnyard grass Echinochloa crusgalli in flats, covered with a piece of cheese cloth and then {5 2'5; 93, 2,233 with about three-fourths inch of soil. The flat was then Dicot ledonous Plant Botanic IN me 1' mustard Brassic kaber sprayed with the compound at a rate of 4 lbs. per acre. The compound was then incorporated into the upper three-fourths inch of soil by lifting up the cheese cloth and mixing the soil in it. The impregnated soil was then replaced over the seed and the evaluation continued as for a regular preemergence test. Table Vlll gives the results.

OOOCOOOOOOOOOO Table VIII 'Herbicidal Eval atio s b il In ti n Kill of Plant Spggigs Example I no 95 o 90 100 40 0 I00 so I00 100 0 70 0 0 2 mo 20 we 20 so so 90 I0 100 so 100 so 0 so 0 0 so 3 100 20 I00 0 95 so 20 50 too 39 I00... .50... .0 3.9 0 0 5 mo I00 8O 90 7o 20 100 100 100 0 60 0 0 I00 8 100 10 100 20 90 100 90 30 90 90 100 0 0 so 70 0 I00 9 100 I 20 100 20 100 100 90 30 100 90 I00 20 0 so 70 0 90 10 l00 10 100 20 100 100 so 0 100 0 100 0 0 90 70 0 80 n 20 20 so 0 30 100 o 0 o 100 0 0 60 60 0 100 I2 .90 30 90 20 9o 100 60 30 100 50 0 6O 50 90 100 I3 I00 0 100 90 90 99 2o 0 I00 0 100 0 so 90 50 0 0 14 0 100 0 20 40 0 0 90 50 50 o 0 10 1s 0 0 100 20 50 6O 0 0 70 100 100 0 20 30 0 40 In field tests, the compound of Example 8 has given 20 solvents are ketone-hydrocarbon mixtures such as good control of ragweed, (Ambrosia spp.), giant foxtail isophorone-xylene. The emulsifying agents used are (Sertaria faberi) and wild lettuce (Lactuca spp.). Such surfactants of the anionic, cationic, or non-ionic types crops as corn, cotton, soybean, tomato, cucumber and mixtures thereof. Representative of the anionic (Cucumis sativa) and peanuts (Arachnis hypogaea) surfactants are fatty alcohol sodium sulfates, calcium have shown tolerance to it. 25 alkylbenzenesulfonates and sodium dialkyl sulfosuccin- Herbicidal activity has been noted for the intermediates Representative of the cationicsare (hi gl1 er a1l yl) ate oxazoline hydrochlorides (Formula VI) and their dimethylbenzyl-ammonium chlorides. Representative free bases. Typical results are given in Table IX for of the nonionics are condensation products of alkylene Preparations B, H and I of Table I at 4 pounds per acre oxides with fatty alcohols, alkyl phenols, mercaptans,

. by the soil incorporation procedure described above. 30 amines or fatty acids, such as dinonyl-phenoxypolye- The plant species designations are the same as those given above as used in Tables VII and VIII. Two additional plant species used in this test were W .lohnsongrass Sorghum halepense X' -p eas Pisum sativum TABLE IX.HERBICIDAL EVALUATIONS BY SOIL thoxyethanol in which there are eight to I00 ether groupings and similar polyethoxy compounds prepared with other hydrophilic groupings, including esters of long chain fatty acids and mannitan or sorbitan, which are reacted MW INCORPORATION, PERCENT KILL OF PLANT SPECIES Prepa- I ration B C D E F G H I K M N O P Q R T U V W X B 50 0 I00 20 70 90 30 20 0 I00 20 0 0 0 100 0 i 90 0 H 2O \l(l0 99 30 I00 0 0 I00 I00 0 I00 40 50 0 0 99 0 90 0 l 95 20 95 0 60 I00 40 0 I00 0 I00 0 0 100 0 0 The compositions of this invention comprise an N (l,l-dialkyl-3-chloroacetonyl)-3-(or -3,4-, -3,5- or -3,4,5-) substituted benzamide together with an agronomically acceptable carrier. By an agronomically acceptable carrier is meant any substance which can be used to dissolve, disperse, or diffuse the chemical within it, without impairing the effectiveness of the toxic agent, which is not permanently deleterious to the soil in any chemical or physical manner and which is usally non-phytocidal to the agricultural crops to be protected. The compositions may be in the form of solutions, emulsifiable concentrates, wettable powders, granules or dusts. One or more liquid or solid carriers may be used for a particular herbicidal composition.

An emulsifiable concentrate is made by dissolving an N-(l,l-dialkyl-3-chloroacetonyl) benzamide in a solvent to which one or more surfactants are added. Suitable solvents or liquid carriers for use in preparing these emulsifiable concentrates may, for example, be found in the hydrocarbon and ketone classes of organic solvents such as xylene, acetone, isophorone, mesityl oxide, cyclohexanone and mixtures 0fth- B e err The following compositions are typical of emulsifiable concentrate formulations when solvents are used..

Parts/ I00 Parts Total N-( l,l-dialkyl-3-chloroacetonyl) benzamide 10 to 35 Solvent 55 to 88 Emulsifying agent 2 to 10 mulations are those which have been rendered agronomically suitable by pulverizing devices and may be organic or inorganic nature. Suitable organic carriers powder formulations:

vention into' a solid carrier such as finely powdered are soybean, walnut or wood flower or tobacco dust; and suitable inorganic ones are clays of the montmorillonite (bentonite), kaolinite or fullers earth types; silicas such as diatomaceous earth and hydrated silica; silicates such as talc, pyrophyllite, or alkaline earth silicates, and calcium and magnesium carbonates. A surfactant or mixture of surfactants is added to the wettable powder formulation. Suitable dispersing agents are sodium lignin sulfonate, sodium formaldehydenaphthalene sulfonate, or sodium N-methyl-N-higher alkyl taurates. Wetting agents useful for this purpose include higher alkylaryl sulfonates such as calcium dodecylbenzenesulfonate, long-chained alcohol sulfates, sodium alkylphenoxypolyethoxyethyl sulfonates, sodium dioctyl sulfosuccinate, and ethylene oxide ad- 5 ducts with fatty alcohols or with higher alkylphenols, such as octylphenoxypolyethoxyethanol in which there are eight to 80 ether groupings and similar polyethoxy compounds made from stearyl alcohol. Operative spreading or adhesive agents include glycerol mannitan laurate or a condensate of polyglycerol and oleic acid modified with phthalic anhydride. Additionally, many of the surfactants discussed above function as spreading and adhesive agents. The active ingredient content of the wettable powders may be in the range of about 20 to 80 percent however, the preferred range of concentration is 50 to 75 percent.

The following compositions are typical for wettable Parts/ 100 Parts Total 20 to 80 I0 to 79 l to 10 .Dust concentrates are made by incorporating an N- (l,l -dialkyl-3-chloroacetonyl) benzamide of this inclays, talc, silica and synthetic silicates, alkaline earth carbonates and diluents of natural origin, such as tobacco dust or walnut shell flour. Granular formulations are made from similar type solid carriers except that the particle size is larger, in the range of 15 to 60 mesh. 4 A small amount of dispersing agent may be incorporated into these solid formulations. The concentration of active ingredients in these dust or granular formulations may be in the range of 0.5 to 15 percent.

It will be seen from the above that the compositions of this invention may contain 20 to 99.5 percent of carrier based on the total weight of the composition, depending on whether it is in the form of a solution, an emulsifiable concentrate, a wettable powder, a dust or a granular formulation.

A particularly convenient method for making solid formulations is to dissolve the active ingredient in a volatile solvent, such as acetone, apply this solution to the solid carrier with thorough mixing, and then remove the solvent by allowing it to evaporate at either normal or reduced pressure.

Generally for use as herbicides the active ingredient is applied at the rate of about 0.5 to 10 or more pounds per acre (0.55 to 11 kilos per hectare) with 1 to 4 pounds per acre (1.] to 4.4 kilos per hectare) preferred.

Representative compounds of Formula I have demonstrated good fungicidal activity for the control of fungi in the class of Phycomycetes. The class of Phycomycetes includes such genera as Phytophthora, Plasmophora, Peronospora and Pseudoperonospora. These compounds have not shown a high degree of fungicidal activity against the classes of fungi known as Fungi Imperfecti and Ascomycetes.

Tests involving the control of late blight, Phytophthora infestans, of potato and tomato were run as described below. Succulent 6-8 inch high (4-5 week old) potato plants and 3-4 inch high tomato plants were used. The plants were sprayed with a 1,200 ppm. solution of the test compound in a solvent system consisting of acetonezmethanokwater at 25:25:50 by hand spraying to just wet the foliage with a minimum of runoff. The plants were then allowed to dry and placed in a greenhouse for 2-3 days. The plants were then subjected to simulated rain by overhead spraying with a garden hose equipped with a Fogg-it nozzle placed about 3 feet above the plants so that approximately 1 inch of rain was delivered in about 2.5 minutes onto the foliage as a fine spray. The plants were then inoculated with a spore suspension of Phytophthora infestans containing 30,0000 40,000 spores per cc. The plants were then placed in a 100 percent humidity chamber at 60 F. for about 36 hours then moved to a F. growing room for 1-2 days. The per cent disease that .had developed in comparison with untreated controls was then read by means of lesion counts. Table X gives the results with representative compounds of this invention.

Table X Control of Phytophthora infestans Disease on Representative compounds of Formula I were found to control the grape downy mildew organism, Plasmopora viticola. In this test 6-8 inch high Seibel grape seedlings were sprayed to run-off using a series of dosages of spray mixtures containing 1,200 ppm. 300 ppm. and ppm. of the test compound. Three replicates for each dosage were used and untreated plants were employed as controls. The plants were held for 24 hours and were then inoculated with a spore suspension of Plasmopora viticola containing about 75,000 spores per cc. The plants were then. held for 1 week under controlled temperature and humidity conditions until the downy mildew disease developed. The percent control was then observed. Table Xl gives the results.

= severe infection. Table gives the results.

Representative compounds of Formula I were evalu ated for the control of downy mildew on broccoli caused by Peronospora parasitica. In this test, "the test compound was dissolved in a 50:50 acetone-methanol solution and diluted with water to give concentrations of 1,200 ppm, 300 ppm. and 150 ppm. of the compound. Each concentration of each compound was i then sprayed to run-off onto three 4-5 inch high broccoli seedlings and the plants allowed to dry. The treated plants were'then weathered in a humidity cabinet overnight and again allowed to dry. The plants were then inoculated with a suspension of Peronospora parasitica spores containing about 10,000 spores per cc. The plants were then held for 6 days to allow the disease lesions to develop and the amount of disease determined based on an index rating of 04 where no infection Table XII Control of Peronospora parasitica Index Rating at Example I200 ppm. 300 ppm. 150 ppm.

In field tests, the compounds of Examples 8 and 14 controlled downy mildew of cucumbers caused by Pseudoperonospora cubensis.

In tests on Alternaria, Cercospora, Helminthosporium, Piricularia and Verticillium genera of fungi, representative compounds of Formula I were low in activity.

Typical oxazoline hydrochlorides of the type of Formula VI have been demonstrated to have fungicidal activity. A test on late blight, Phytophthora infestans, of tomato was conducted similarly to that described above for the data in Table X except subjecting the plants to simulated rain was omitted. The amount of disease control was recorded by the following rating system 18 Table XIII gives the results for typical preparations of compounds of Formula VI and their free bases at two dosage rates.

Table XIII Control of Phytophthora lnfestans Rating at Preparation I200 ppm. 150 ppm.

B A A D B C E A A G A A J A A- M A- B N A- 8+ a See Table l Oxazolinesalts conforming to the structure 1' 1 20 a e (i e Y' O (Ha1)CH(Hal)| wherein R, R X, X and Y have the meanings given above for Formula I and Hal is bromine or chlorine or a mixture thereof and their free bases have also demonstrated excellent fungicidal activity.

A compound of Formula IX where I-Ial is bromine may be made by a bromination sequence of compounds in which C1 in the equations given above is replaced by Bra. The hssqpstisnidepist his 1' 1 Y C(O)NHGCECH Bra so ven HN--- --R 9 $6 (I; B! B1! Y =CHBr 0 x (X) Rt X I HN- --R g9 l r Y /0 (Br)CHBr; neutralization O (XI) t t-slat- Y C (Br)CHBr| 0 X (XII) The reaction conditions for the bromination are the same as for the chlorination.

Typical structures corresponding to Formula IX are 5 Preparation 0 2-(3,5-dlchlorophenyl)-4.4-dimethyl-5- ehloro-S-dichlommethyl-oxuzoline hydrochloride (nee Example l3u above) Preparation-Continued 7 P 2-(3,5-dichlorophenyl)-4,4-dimethyl- 5-chloro-5-dichloromethyl-oxazoline (see Example 13a above) 2-(3,S-dichlorophenyl)-4,4-dimethyl-5- bromo-S-dibromethyl-oxazoline hydrobromide. This is a solid melting at 2l0 C. (with decomposition). It

was found to contain by analysis 25.0% C,

' 1.9% H, 54.5 Br, 11.9% Cl, 25% N and 3.5% 0; calculated for C, H, Br Cl,NO'HBr is 24.6% C, l.9% H, 54.6% Br, l2.l% Cl, 2.4% N and 2.7% O.

2-(3,5-dichlorophenyl)-4,4-dimethyl-5- bromo-S-dibromomethyl-oxazoline. This is a solid melting at l-l25" C. (with decomposition). It was found to contain by analysis 29.4% C, 2.0% C, 2.0% H, 46.9% Br, l4.l% Cl, 2.9% N and 3.9% 0; calculated for C H Brhd 3Cl NO is 29.1% C, 2.0% H, 48.4% Br, l4.3% CI, 2.8% N and 3.2% 0.

Table XIV gives the fungicidal results for typical compounds of Formula IX and their free bases when evaluated on Phytophthora infestans by the technique described for Table XIII and on Plasmopora viticola by the technique described for Table XI.

In persistency-type tests wherein the treated plants were weathered by means of rain before inoculation Preparation Q gave excellent results for the control of Phytophthora infestans and Preparation R gave excellent results for the control of Plasmopora viticola.

For use as fungicides the N-( 1,1-dialkyl-3- chloroacetonyl) benzamides and the oxazoline structures of Formula VI and IX are usually formulated. Emulsifiable concentrates, flowable emulsion concentrates and wettable powders are typical formulations. They may also be dissolved in water-miscible solvents to give solutions which may be easily extended with water. Dilute sprays of the compounds may be applied at concentrations of 0.05 to 10 pounds (0.023 to 4.5 kilos) per 100 gallons (378 liters) of spray and preferably at 0.1 to 2 pounds (0.045 to 0.9 kilos) per 100 gallons of spray. In more concentrated sprays, the active ingredient is increased by a factor of two to 12. With dilute sprays, applications are usually made to the plants until run-off is achieved, whereas with more concentrated sprays the materials are applied as mists. For practical purposes, the compounds of this invention should be used as foliar fungicides only on crops which are tolerant to an amount which is fungicidally effective.

When a chemical preparation results in a mixture of products, such as when the chlorination of a compound of Formula Vlll gives more than one product, the mixture may be used as such without separation of the individual components.

The compounds of this invention may be utilized as the sole biocidal agent or they may be employed in conjunction with other biocidal agents such as bactericides, fungicides, herbicides, insecticides. miticides and v comparable pesticides.

Other herbicides which can be incorporated to pro-- vide additional advantages and effectiveness include:

Carboxylic Acids and Derivatives 2,3,6-trichlorobenzoic acid and its salts 2,3,5,6-tetrachlorobenzoic acid and its salts 2-methoxy-3,5,6-trichlorobenzoic acid and its salts 2-methoxy-3,-dichlorobenzoic acid and its salts 2-methyl-3,6-dichlorobenzoic acid and its salts 2,3-dichloro-6-methylbenzoic acid and its salts 2,4-dichlorophenoxyacetic acid and its salts and esters 2,4,5-trichlorophenoxyacetic acid and its salts and esters (2-methyl-4-chlorophen0xy)acetic acid and its salts and esters 2-(2,4,5-trichlorophenoxy)propionic acid and its salts and esters 4-(2,4-dichlorophenoxy)butyric acid and its salts and I BSICI'S 4-(2-methyl-4-chlorophenoxy)butyric acid and its salts and esters 2,3,6-trichlorophenylacetic acid and its salts 3,6-endoxohexahydrophthalic acid dimethyl 2,3,5,6-tetrachloroterephthalate trichloroacetic acid and its salts 2,2-dichloropropionic acid and its salts 2,3-dichloroisobutyric acid and its salts Carbamic Acid Derivatives ethyl N,N-di(n-propyl)thilcarbamate propyl N,N-di(n-propyl)thiolcarbamate ethyl N-ethyl-N-(n butyfithiolcarbamate propyl N-ethyl-N-(n-butyl)thiolcarbamate 2-chloroallyl N,N-diethyldithiocarbamate N-methyldithio-carbamic acid salts ethyl l-hexamethyleneiminecarbothiolate isopropyl N-phenylcarbamate isopropyl N-(m-chlorophenyl)carbamate 4-chloro-2-butynyl N-(m-chlorophenyl)carbamate methyl N-(3,4-dichlorophenyl)carbamate Phenols dinitro-o-(sec.-butyl)phenol and its salts pentachlorophenol and its salts Substituted Ureas 3-( 3 ,4-dichlorophenyl)- l l -dimethylurea 3-(4-chlorophenyll l-dimethylurea Substituted Triazines 2-chloro-4,6-bis(ethylamino)-s-triazine 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis( methoxypropylamino )-s-triazine 2-methoxy-4,6-bis(isopropylamino)-s-triazine 2-chloro-4-ethylamino-6-(3-methoxypropylamino)-stt ne 2-methylmercapto-4,6-bis(ethylamino)-s-triazine 2-metylmercapto-4-ethylamino-6-isopropylamino-striazine 2-chloro-4,6-bis(isopropylamino)-s-triazine 2-methoxy-4,6-bis(ethylamino)-s-triazine 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2 -methylmercapto-4-(2-methoxyethylamino )-6-isopropylamino-s-triazine Diphenyl Ether Derivatives 2,4-dichloro-4'-nitrodiphenyl ether 2,4,6-trichloro-4'-nitrodiphenyl ether 2,4-dichloro-6-fluoro-4-nitrodiphenyl ether 3-methyl-4-nitrodiphenyl ether 3,5-dimethyl-4-nitrodiphenyl ether 2,4'-dinitro-4-trifluoromethyldiphenyl ether Other Organic Herbicides 2-chloro-N,N-diallylacetarnide N-( l ,1-dimethyl-2-propynyl)-3,S-dichlorobenzamide maleic hydrazide 3-aminol ,2,4-triazole monosidum methanearsonate disodium methanearsonate N,N-dimethyl-a,a-diphenylacetamide N,N-di-(n-propyl)-2,6-dinitro-4-trifluoromethylaniline N,N-di-(n-propyl)-2,6-dinitro-4-methylaniline N,N-di-(n-propyl)-2,6-dinitro-4-methylsulfonylaniline (2,4-dichlorophenyl)-0-methyl-isopropylphosphoramidothioate 4-amino-3,5,-trichloropicolinic acid 2,3-dichloro-l ,4-naphthoquinone di(methoxythiocarbonyl)disulfide 6,7-dihydrodipyrido[ l,2-a:2',l '-c]pyrazidinium salts 1,1 -dimethyl-4,4-bipyridinium salts 3 ,4,5 ,6-tetrahydro-3 ,5-dimethyl-2-thio-2H-1,3 ,5- thiadiazine Other fungicides which may be combined with the compounds of this invention include dithiocarbamate and derivatives such as ferric dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), manganese ethylenebisdithiocarbamate (maneb) and its 00- 65 I ordination pr oduct with zinc ion, iinc ethylenebisdithfl ocarbamate (zineb), tetramethylthiuram dislufide (thiram) and 3,5-dimethyl- 1 ,3 ,5 ,ZH-tetrahydrothiadiaginq 2-thione; nitrophenol derivatives such as dinitro-( lmethylheptyl)phenyl crotonate (dinocap), 2-sec-butyl- 4,6-dinitrophenyl 3,3-dimethyl-acrylate (binapacryl) and 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic structures such as N-trichloromethylthiotetrahydrophthalimide (captan), N-trichloromethylthiophalimide (folpet), 2-heptadecyl-2-imidazoline (glyodin), 2,4-dichloro-6-(o-chloro-anilino)-s-triazine, diethyl phtalimidophosphorothioate, S-amino-l- [bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4- triazole, 2,3-dicyano-1,4-dithia-anthraquinone (dithianon), 2-thio-l ,3-dithio [4,5-b]quinoxaline (thiuir oxl, kbutylca rbamoyl)-2-benzimidazole car; bamic acid methyl ester (benomyl), 4-(2- chlorophenylhydrazone)-3-methyl-5-isoxazolone and bis(p-chlorophenyl)-3-pyridinemethanol; and miscellaneous fungicides such as dodecylquanidine acetate (dodine), 3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2- hydroxyethyl1glutarimide (cycloheximide), phenylmercuric acetate, N-ethylmercuri-l,2,3,6-tetrahydro- 3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide, phenylmercuric monoethanolammonium lactate, 2,3- dichlorol ,4-naphthoquinone, pyridine-Z-thioll oxide, Bordeaux mixture and sulfur.

We claim:

1. A method for controlling undesirable plant growth comprising applying to the area to be controlled a herbicidal amount of a composition, at the rate of about 0.5 to 10 poundsper acre, comprising (1) an active ingredient having the formula Rt r wherein R and R are methyl or ethyl;

X and X are hydrogen, bromo, chloro, fluoro, methyl, ethyl or trifluoromethyl with the proviso that only one may be hydrogen; and Y is hydrogen, bromo, chloro, fluoro or methyl, and the free bases thereof, together with (2) a carrier.

2. A method for controlling undesirable plant growth comprising a herbicidal amount of a composition according to claim 1, wherein R and R of said active ingredient are methyl.

3. A method for controlling undesirable plant growth comprising applying to the area to be controlled a herbicidal amount of a composition according to claim 1- wherein said active ingredient is 2-(3,5- dichlorophenyl)-4,4-dimethyl-S-chloromethyleneoxazoline hydrochloride or it free base.

4. A method according to claim 1 wherein the active ingredient of the herbicidal composition is from 0.5 to percent of the composition and is applied at the rate of about 1 to 4 pounds per acre. 

2. A method for controlling undesirable plant growth comprising a herbicidal amount of a composition according to claim 1, wherein R1 and R2 of said active ingredient are methyl.
 3. A method for controlling undesirable plant growth comprising applying to the area to be controlled a herbicidal amount of a composition according to claim 1 wherein said active ingredient is 2-(3,5-dichlorophenyl)-4,4-dimethyl-5-chloromethylene-oxazoline hydrochloride or it free base.
 4. A method according to claim 1 wherein the active ingredient of the herbicidal composition is from 0.5 to 80 percent of the composition and is applied at the rate of about 1 to 4 pounds per acre. 